Cellulose derivative composition



Patented Sept. 4,

PATENT OFFICE CELLULO SE DERIVATIVE COMPOSITION George De Witt Graves and Walter Eastby Lawson, Wflmington, Del., assignors to E. I. du Pont deNemourst Company, Wilmington, Del., a corporation of Delaware No Drawing. Application December 8, 1932,,

Serial No. 646,298

16 Claims.

This inventionrelates to cellulose derivative compositions, and more particularly, to such compositions including as plasticizers therefor organic polycarboxylic acid esters containing an esterified higher alkyl group. This application is a continuation in part of Graves and Lawson United States application'Serial No. 543,387, filed June 10, 1931, entitled Cellulose derivative compositions.

An object of the present invention is to provide cellulose derivative compositions of improved water resistance. A further object is to provide cellulose derivative compositions which are substantially permanently flexible, and having im- 115 proved durability. Other objects will be apparent from the description of the invention hereinafter given.

The above objects are accomplished according to the present invention by the use of esters 20 of organic polycarboxylic acids, at least one acid hydrogen atom of which has beenreplaced by'a normal saturated aliphatic radical containing from -15 carbon atoms, inclusive, as a plasticizer for the cellulose derivative. I

The invention contemplates within its'tscope the use of esters of any of the organic polycarboxylic acids, whether belonging to the aromatic or aliphatic series. One or more of the carboxylic hydrogen atoms is replaced by a normal saturated 80 aliphatic radical containing from 10-15 carbon atoms corresponding to the following listof alcoholsz n-decyl CmHziOH n-undecyl C11H23OH lauryL, CHHZBOH. n-tridecyl C13H27OH myristyl C14H29OH, n-pentadecyl C15H31OH.

The esters may. contain only one of the" above listed alkyl groups and may contain a free car boxylic' acid group. Alternatively, an ester containing one normal saturated aliphatic group having 10-15 carbon atoms, may have another carboxylic acid group esterified with any other alcohol. esters of polycarboxylic acids in which more than one acid hydrogen is replaced with a normal saturated aliphatic group having from 10-15 carbon.

atoms. Accordingly, the inventionincludes the use of neutral esters of organic polycarboxylic' acids in which all of the carboxylic acid groups are esterified, such esters containingone or more The invention also includes the use of fled to yield the esters included within the present invention'may contain two or more carboxylic acid groups. The following organic acids are named as typical of those which may be used: orthophthalic, terephthalic, oxalic, succinic, adipic, ,maleic, fumaric, tartaric, malic, citric, quinolinic, vtrimesic, .pyromellitic, naphthalic, naphthalene tetracarboxylic, tricarballylic, hexahydrophthalic, hydroxy phthalic, uvitic, tetrachlorophthalic, sebacic, itaconic, and pimelic.

These esters are preferably made by bringing together the desired alcohols and acids (or where theanhydride of the polycarboxylic acid is available it may be used in lieu'of the acid) and then heating the mixture, preferably attemperatures above 100 C. so that the water produced by the esterification will boil oil and thus permit the reaction to go to completion. The removal of this water may be assisted'by adding to the esterification mixture a carrier liquid, such as benzene or toluene, which will distill out with the water at a temperature below 100 C., in which case the esterification may becarried on at a lower temperature than would otherwise be used. An inert gas, such as carbon dioxide, may be continua ously passedthrough the reacting mixture to accomplislrthe same purpose, namely, to facilitate the removal of water.

The following examples are given to illustrate typical molding and lacquer cellulose derivative compositions employing the above described esters as plasticizers for the cellulose derivative:--

MOLDING COMPOSITIONS Example 1 r Parts Cellulose nitrate 100 Dilauryl phthalate 35 Example 2 Parts Cellulose nitrate Dilauryl phthalateul 20 Tricresyl phosphate 15 Example 3 I 7 Parts Cellulose acetate 100 Dilauryl phthalate 30 3 Example 4 Parts Cellulose acetate 100 Dilauryl phthalate 20 Triacetin; 15

Example 5 Parts Cellulose nitrate 100 Lauryl butyl phthalate 35 Example 6 Parts Cellulose nitrate 100 Cyclohexyl decyl phthalate 35 LACQUER COMPOSITIONS Example 7 v Parts Cellulose nitrate 12 Damar -1 3 Lauryl butyl adipate 4 Castor oil 2.6 Solvent 166.5

Example 8 Parts Benzyl cellulose 4 D'ilauryl succinate 1 Hexyl caproate 1 Solvent 24 Example 9 Parts Benzyl cellulose 4 Damarn 1 Didecyl adipate 1 Solvent r 24 Example 10 Parts Cellulose nitrate 12.0 Damar 3.0 'Dilauryl 'adipate 4.0 Pigment 16.3 Castor oil 2.6 Solvent 161.6

Example 11 Parts Cellulose nitrate 12 Damar 3 Didecyl phthalate 4 Castor -oil 2.6 Solvent -11. 166.5

polybasic acid or phenol-formaldehyde resins,

pigments, and the like, may be included in these compositions.

Not only dicarboxylic acid esters may beused,

as shown in the above compositions, but also tri- 'carboxylic, or higher polycarboxylic acid esters may be used, such as trilauryl citrate. Thecellulose derivative compositions containing the esters described above may be used either as lacquersor as molding compositions, as shown in the above examples, or as dopes for use in the preparation of coated fabrics. In the case of the lacquers and the dopes, they may be applied by spraying, brushing; flowing, spreading under adoctor knife, or by other suitablemethodsof ap- 'plication. When used as molding compositions thin films which fin'd'use' as "strengthening layers They also can be pressed.

for safety glass and in other applications where materials of this sort are regularly used.

The cellulose derivative compositions, which may include esters or ethers, are characterized by the fact that they are exceptionally resistant to water, since the plasticizers used in these compositions areall esters of higher aliphatic alcohols having substantial Water resistance. The compositions are exceptionally durable and substantially permanently flexible, due to the use of the herein described esters as plasticizers. These esters have higher molecular weights than the commonly used plasticizers and, consequently, have higher boiling points and lower vapor pressures, properties which insure substantially permanent retention of the plasticizer in the cellulose derivative composition, and hence a flexible and durable product. The esters are satisfactorily compatible with cellulose derivatives and give compositions of exceptionally favorable properties.

As many apparently widely different embodiments of this invention may be made without de-T parting from the spirit and scope thereof, it is to be understood that we do not limit ourselves to the specific embodiments thereof except as defined in the appended claims.

We claim;

1. A composition of matter comprising a cellulose derivative and an ester of an organicpolycarboxylic acid, at least one acid hydrogen atom of, which has been replaced by the radical of a normal primary monohydric aliphatic alcohol.

containing from 10-15 carbon atoms, inclusivelf 2. A composition of matter comprising a cellulose derivative and an neutral. ester of an organic polycarboxylic acid, at least one acid hydrogen atom of which has been replaced by the radical of a normal primary monohydric aliphatic alcohol containing from 10-15 carbon. atoms, inclusive..

3.,Acomposition of matter comprising a cellulose derivative and an ester of. an organic polycarboxylic acid, eachof the acid hydrogen atoms.

of whichv have beenreplaced by the radical of a normal primary monohydric aliphatic alcohol containing from. 10-15 carbon atoms, inclusive.

4. A composition. of matter comprising a cellulose derivative and an'ester of an organic dicarboxylic acid, at, least one acid. hydrogen atom oi which has been replaced by the radical of a. normal primary monohydric aliphatic alcohol j containing from 10-15 carbon atoms, inclusive.

5. A compositionof. matter comprisinga cellu-' lose derivative and a neutral ester. of. an' organic dicarbox-ylic acid,.at least one. acidhydrogen atom of which". hasbeen replaced by the. radical'oii' a normal. primary monohydric. aliphatic alcohol containing from.10-15 carbon. atoms, inclusive. l

6. A composition of matter comprising. a cellulose derivative and an ester of an organic di'c'ar-, boxylic acid, each of the acid hydrogen atoms of which have been replaced by theradi'cal of a normal primary monohydric aliphatic alcohol containing from 10-15carbon atoms, inclusive.

7'. A composition of matter comprising a cellu-' lose derivative and an ester of aphthalic acid,".at

least one acid'hydrogen atom of which has been I lose derivative and a neutral'ester offa phthalic acid; atleast one acid hydrogen atom of which has been replaced by the radical of 'anormalprimary 8. A composition of matter comprising a cellu monohydric aliphatic alcohol containing from 10-15 carbon atoms, inclusive.

9. A composition of matter comprising a cellulose derivative and an ester of a phthalic acid,

each of the acid hydrogen atoms of which have been replaced by the radical of a normal primary monohydric aliphatic alcohol containing from 10-15 carbon atoms, inclusive.

10. A composition of matter comprising a cellulose derivative and a normal primary decyl phthalate.

11. A composition of matter comprising a cellulose derivative and di-normal primary decyl phthalate.

12. A composition of matter comprising a cellulose derivative and an ester of adipic acid, at least one acid hydrogen atom of which has been replaced by the radical of a normal primary monohydric aliphatic alcohol containing from 10-15 carbon atoms, inclusive.

13. A composition of matter comprising a cellulose derivative and di-normal primary decyl adipate.

14. A composition of matter comprising a cellulose derivative and normal primary decyl cyclohexyl phthalate.

15. A composition of matter comprising a cellulose derivativeand an ester of an organic dicarboxylic acid of the group consisting of phthalic and adipic acids, at least one acid hydrogen of which has been replaced by a normal primary, decyl radical.

16. A composition of matter comprising a cellulose derivative and an ester of an organic dicarboxylic acid of the group consisting of phthalic and adipic acids, at least one acid hydrogen of which has been replaced by the radical of a normal primary monohydric alcohol containing from ten to fifteen carbon atoms, inclusive. 

